Ethics, Toxicity, Ecotoxicity, Persistence, Bioaccumulation and Green Chemistry Terry Collins Central Catholic High School, September 21, 2005, Pittsburgh PA Ethics, Toxicity, Ecotoxicity, Persistence, Bioaccumulation and Green Chemistry Terry Collins Central Catholic High School, September 21, 2005, Pittsburgh PA Western Civilization is not sustainable as it is currently constituted flawed technologies are an important component of the sustainability dilemma Western Civilization is not sustainable as it is currently constituted flawed technologies are an important component of the sustainability dilemma Altered Nature of Human Action All previous ethics[have been based upon the premises]that the human condition, determined by the nature of man and the nature of things,was given once for all; that the human good on that basis was readily determinable; and that the range of human action and therefore responsibility was narrowly circumscribed. [But] with certain development of our powers the nature of human action has changed, and [given rise to] a whole new dimension of ethical relevance for which there is no precedent in the standards and canons of traditional ethics. The Imperative of Responsibility: Finding an Ethics for the Technological Age, Hans Jonas, U. Chic. Press, 1984 A new reflection on ethical principlesincluding such that, for lack of application, could hitherto remain silentis required for coping with those issues. The Imperative of Responsibility: Finding an Ethics for the Technological Age, Hans Jonas, U. Chic. Press, 1984 The altered, always enlarged nature of human action, with the magnitude and novelty of its works and their impact on mans global future, raises more issues for which past ethics, geared to the direct dealings of man with his fellow men within narrow horizons of space and time, has left us unprepared. Its axiom is that responsibility is a correlate of power and must be commensurate with the latters scope and that of its exercise. The Imperative of Responsibility: Finding an Ethics for the Technological Age, Hans Jonas, U. Chic. Press, 1984 The lengthened reach of our deeds moves responsibility, with no less than mans fate for its object, into the center of the ethical stage. Accordingly, a theory of responsibility, lacking so far, is set forth for both the private and the public sphere. For its discharge today, therefore, we need lengthened foresight, that is, scientific futurology. Consequently, an imaginative heuristics of fear replacing the former projections of hope, must tell us what is possibly at stake and what we must beware of. The Imperative of Responsibility: Finding an Ethics for the Technological Age, Hans Jonas, U. Chic. Press, 1984 Even at its best, however, such an extrapolation from presently available data will always, in certainty of prediction, fall short of the causal pregnancy of our technological deeds. The magnitude of those stakes, taken together with the insufficiency of our predictive knowledge, leads to the pragmatic rule to give the prophecy of doom priority over the prophecy of bliss. What we must avoid at all cost, is determined by what we must preserve at all cost, and this in turn is predicated on the image of man we entertain. Formerly, this image was enshrined in the teachings of revealed religions. With their eclipse today, secular reason must base the normative concept of man on a cogent, at least persuasive, doctrine of general being: metaphysics [the branch of philosophy that examines the nature of reality] must underpin ethics. Hence, a speculative attempt is made at such underpinning of mans duty to himself, his distant posterity, and the plenitude of terrestrial life under his dominion. The Imperative of Responsibility: Finding an Ethics for the Technological Age, Hans Jonas, U. Chic. Press, 1984 That attempt must brave the veto of reigning analytical theory against all attempts of this kind and indeed cannot hope for more than a tentative result. But dare it we must. A philosophy of nature is to bridge the alleged chasm between scientifically ascertainable is and morally binding ought. The thus-gained conception of objective imperatives for man in the scheme of things enables us to discriminate between legitimate and illegitimate goal-settings to our Promethian [boldly creative or defiantly original in behavior or actions] power (a distinction encompassing but surpassing that between realistic and unrealistic goals). This discrimination is elaborated in assessing the potentials of progress up to the most ambitious idea of it contemporary utopianism as represented by the Marxian alliance with technology. Against the immodesty of its goals, which maximize the inherent dangers of overstraining nature, the more modest and fitting goal is set to save the survival and humanity of man from the excesses of his own power. The Imperative of Responsibility: Finding an Ethics for the Technological Age, Hans Jonas, U. Chic. Press, 1984 A whole new dimension of ethical relevance The Imperative of Responsibility: Finding an Ethics for the Technological Age, Hans Jonas, U. Chic. Press, 1984 A whole new dimension of ethical relevance The Imperative of Responsibility: Finding an Ethics for the Technological Age, Hans Jonas, U. Chic. Press, 1984 Today, because of science and technology, individual power projects into both time and space much further than ever before. Ethics is about the forces that guide human action. Science, especially chemistry, has become completely intertwined with human action. Accurate analysis of any human action in the developed world is impossible absent an examination the influence of chemistry on that action, from the way we communicate, educate ourselves, feed ourselves, protect our health, and even to the way we procreate. Ethical principles need to be reinterpreted to recognize the reality of the vast power we now have over life and the environment because of science and technology. Thus, chemistry is inextricably intertwined with ethics! A healthy education in chemistry should contain a significant analysis of sustainability ethics. Today, because of science and technology, individual power projects into both time and space much further than ever before. Ethics is about the forces that guide human action. Science, especially chemistry, has become completely intertwined with human action. Accurate analysis of any human action in the developed world is impossible absent an examination the influence of chemistry on that action, from the way we communicate, educate ourselves, feed ourselves, protect our health, and even to the way we procreate. Ethical principles need to be reinterpreted to recognize the reality of the vast power we now have over life and the environment because of science and technology. Thus, chemistry is inextricably intertwined with ethics! A healthy education in chemistry should contain a significant analysis of sustainability ethics. The idea that our civilization is not sustainable, now broadly accepted in a growing consensus, implies that someone is responsible for fixing things. If unsustainable technologies are part of the problem, the technical leadership is clearly responsible for fixing this part. The leadership must first ask, for each identified problem, if solutions are conceivable. If the answer is affirmative, the responsibility of the leadership translates into a duty to engage energetically in finding the solutions. If the answer is negative, their responsibility translates into a duty to alert the civilization to move away from the dependence that is undermining it. The leadership must first ask, for each identified problem, if solutions are conceivable. If the answer is affirmative, the responsibility of the leadership translates into a duty to engage energetically in finding the solutions. If the answer is negative, their responsibility translates into a duty to alert the civilization to move away from the dependence that is undermining it. The Fundamental Green Chemistry Concept Risk = f 1 (exposure) f 2 (hazard) Paul Anastas and John Warner T, J. Collins, The Importance of Sustainability Ethics, Toxicity and Ecotoxicity in Chemical Education and Research, Green Chemistry, 2003 (August), G51-G52 To teach green chemistry properly, green chemists must develop an adequate understanding of toxicity and ecotoxicity [of f 2 (hazard)] and incorporate this into the basic course material of chemistry. The Chemical Goals for Sustainability The Chemical Goals for Sustainability Safe Energy Safe Energy Renewable Feedstocks Renewable Feedstocks Pollution Reduction New chemistry for solar-to-electrical or solar-to- chemical energy conversions Economical feedstocks for chemical and polymer industries from plants Move the elemental composition of technology closer to biochemistry to eliminate persistent environmentally mobile pollutants Solar Stirling Engines The stakes of failing to address toxicity and ecotoxicity are incredibly high. Decrease in anogenital distance among male infants with prenatal phthalate exposure, Shanna Swan et al., Environmental Health Perspectives on-line May 27, 2005 Exposure to methoxychlor and vinclozolin produces male reproductive problems down 4 generations, Michael Skinner et al., Science 2005, 308, Perinatal exposure to low levels of the environmental anti-androgen vinclozolin alters sex-differentiated social play and sexual behaviors in the rat, Vincent Markowski, et al., Environmental Health Perspectives, 2005, 113, Use of di(2-diethylhexyl)phthalate-containing medical products and urinary levels of mono(2- diethylhexylphthalate) in neonatal intensive care units, Howard Hu et al., Environmental Health Perspectives, on-line, June 10, Decrease in anogenital distance among male infants with prenatal phthalate exposure, Shanna Swan et al., Environmental Health Perspectives on-line May 27, 2005 Exposure to methoxychlor and vinclozolin produces male reproductive problems down 4 generations, Michael Skinner et al., Science 2005, 308, Perinatal exposure to low levels of the environmental anti-androgen vinclozolin alters sex-differentiated social play and sexual behaviors in the rat, Vincent Markowski, et al., Environmental Health Perspectives, 2005, 113, Use of di(2-diethylhexyl)phthalate-containing medical products and urinary levels of mono(2- diethylhexylphthalate) in neonatal intensive care units, Howard Hu et al., Environmental Health Perspectives, on-line, June 10, 2005. Percentage of offspring affected Day of exposure after conception Males with areolae Abnormal seminal vesicles Hypospadias Small prostate Abnormal bladder Paul Foster and Martha Harris, Toxicol Sci, 2005, 1591 Exposure to anti-androgen, Flutamide Courtesy of J. Peterson Myers Courtesy of J. Peterson Myers Historical analyses building from the anecdotal, to the epidemiology, to the molecular level understanding importance. Toxicity testing as an integral component of chemical research guidance. More interdisciplinary research involving chemists and toxicologists synergy. An outright rejection of spin obligation. Historical analyses building from the anecdotal, to the epidemiology, to the molecular level understanding importance. Toxicity testing as an integral component of chemical research guidance. More interdisciplinary research involving chemists and toxicologists synergy. An outright rejection of spin obligation. How might chemists learn how to avoid known toxicity/ecotoxicity in the design of new products and processes? Discovery of Lead Toxicity Sweet Poison Josef Eisinger Natural History, 7/96 The Bastion of Ulm Goslar Evidence belies the idea that Pb is part of the natural human intake! Lead Poisoning May Have Doomed Beethoven A house painter affected by chronic lead poisoning. Wasted muscles and wrist-drop are tell-tale symptoms of lead poisoning. Lead Industry Advertises through Children Deceit and Denial, Markowitz and Rosner The cover of the National Lead Companys trade magazine conveys the message that children can be encouraged to use lead paint safely on toys. (Dutch Boy Painter, December 1928) Deceit and Denial, Markowitz and Rosner Even after WWII, lead was promoted as a boon to children. Here, National Lead tells parents that lead solder is not a problem, even in canning evaporated milk meant for babies. (Saturday Evening Post, February 23, 1946) Lead Industry Advertises through Children Some People of Lead History Deceit and Denial, Markowitz and Rosner Felix Wormser, General Secretary Lead Industries Association (LIA) from 1928 to 1947, led the industrys battle against negative publicity. Joseph Aub, Harvard University Lead Researcher supported by LIA, regularly underplayed lead paint toxicity. Robert Kehoe, University of Cincinnati Kettering Labs physiologist who helped formulate the lead industries position on toxicity of PbEt 4 Aub and Kehoe dominated lead toxicity research for three decades from the 1920s. Herbert Needleman, academic pediatrician at Childrens Hospital in Philadelphia, later psychiatrist at Harvard and then University of Pittsburgh, leader in showing toxic effects of low level lead in children. Felix Wormser, General Secretary Lead Industries Association (LIA) from 1928 to 1947, led the industrys battle against negative publicity. Joseph Aub, Harvard University Lead Researcher supported by LIA, regularly underplayed lead paint toxicity. Robert Kehoe, University of Cincinnati Kettering Labs physiologist who helped formulate the lead industries position on toxicity of PbEt 4 Aub and Kehoe dominated lead toxicity research for three decades from the 1920s. Herbert Needleman, academic pediatrician at Childrens Hospital in Philadelphia, later psychiatrist at Harvard and then University of Pittsburgh, leader in showing toxic effects of low level lead in children. Metabolism of Lead in Humans Lead ingested ( g/day) Skeleton (90%) t 1/2 25 years Blood Kidney Urine GI tract Feces Lungs Lead inhaled Soft tissues (liver, brain, pancreas, kidneys, bone marrow) t 1/2 40 days (8% adult, (92% adult, 75% children) Lead is a systemic poison 25% children, perhaps 50%) (Estimate: 20400 g/day) Environmental Toxicology: Biological and Health Effects of Pollutants, 2nd Edn. Ming-Ho Yu, CRC Press, Boca Raton 2005 National BLLs Nearly a million US children are at risk from lead poisoning (BLLs > 10 g.dL -1 ) and specific groups of children are at greatest risk. Casarett and Doulls Toxicology: the basic science of poisons, 6th Edn. Curtis D. Klassen, McGraw-Hill, New York, 2001 BLL above 10 g/dL (% children) Age of residence (year built) Biological Effects of Lead Environmental Toxicology: Biological and Health Effects of Pollutants, 2nd Edn. Ming-Ho Yu, CRC Press, Boca Raton 2005 in plants, Pb inhibits electron transport in corn mitochondria, depresses respiratory rate in germinating seeds, and inhibits various enzyme systems. Pb has a high affinity for the sulfhydryl group (SH). Enzymes with function dependent upon the SH group may be inhibited by mercaptide formation leading to inactivation. 2RSH + Pb 2+ RSPbSR + 2H + egs: adenyl cyclase: catalyzes conversion of ATP to cyclic AMP needed in brain neurotransmission, aminotransferase involved in transamination, important in protein metabolism in mammals, Pb 2+ can compete with Ca 2+ for entry at the presynaptic receptor because Ca 2+ evokes release of acetylcholine (ACh) across the synapse, inhibition induces a decreased end-plate potential. The miniature end-plate potential release of sub-threshold levels of ACh is increased. adverse effects on nucleic acids leading to decreased or increased protein synthesis. Pb decreases aminoacid acceptance by tRNA and the ability of tRNA to bind to the ribosome Pb causes dissociation of ribosomes Pb inhibits ALAD and ferrochelatase both involved in heme biosynthesis ferrochelatase catalyzes the incorporation of Fe 2+ into protophyrin IX Scheme of Heme Biosynthesis Showing Sites Where Pb Has an Effect Casarett and Doulls Toxicology: the basic science of poisons, 6th Edn. Curtis D. Klassen, McGraw-Hill, New York, 2001 Mitochondrion Succinyl CoA + glycine ALA dehydratase ALA-D ALA synthetase ALA-S -aminolevulinic acid (ALA) Porphobilinogen (PBG) Uroporphyrinogen I Heme Ferrochelatase + Fe 2+ Uroporphyrinogen IIICoproporphyrinogen III Protoporphyrin IX Site of Pb inhibition Pb Cytoplasm Pb Copro III Coproporphyrinogen oxidase Heme Oxidase microsomal Pb Bilirubin + Fe Cytochrome C + Fe 2+ Pb Reproductive Toxicology of Lead MALE Pb 2+ (also Cd 2+ ) are well known reproductive toxicants exposure has been associated with infertility and chromosomal damage in sperm. Cd 2+ can cause testicular necrosis, probably by decreasing blood flow to the testes. Other male reproductive toxicants include: ethanol, which causes delay in testicular development and may effect supporting cells the pesticides, kepone and DDT, the solvent, CS 2, and tobacco smoke (smokers have a higher % of abnormal sperm cells than non-smokers). FEMALE Pb poisoning associated with reduced fertility, miscarriages and stillbirth since antiquity cytotoxic substances such as antineoplastic agents, heavy metals, polycyclic aromatic hydrocarbons (PAHs), or radiation may damage oocytes, particularly in adult women. some cytotoxic substances, e.g., PAHs, must be metabolized to produce toxicity the activation can take place via cytochrome P450 in the ovaries (epoxide formation). Toxic PAH metabolites destroy primary oocytes, providing one explanation for the observation that smoking may lead to early menopause. other toxicants include pesticides, chlorinated hydrocarbons, and aromatic solvents Principles of Toxicology. Karen F. Stine & Thomas M. Brown, CRC Press, Boca Raton 1996 The Institute for Green Oxidation Chemistry Novel Funding Approaches World Leading Research in Green Oxidation Catalysis Training Next Generation of GC Leaders New Chemistry Curricula for Sustainability biochemically common elements prototype v. low toxicity TAML Catalyst Features beginning of dial-a-lifetime catalysis economical to synthesize water-soluble usable from pH 1 to 14.5 efficient users of peroxide fast peroxidase/slow catalase efficient users of peroxide fast peroxidase/slow catalase 10 US patents, 86 counting foreign nationalizations effective at 0.1 to 4 ppm = nM to low M ~ 100 companies have CDA with Carnegie Mellon University next step is multi-ton production one license in place Textiles dye bleaching, effluent decolorization Textiles dye bleaching, effluent decolorization Pulp and Paper pulp bleaching, effluent smell, organochlorine and color removal Pulp and Paper pulp bleaching, effluent smell, organochlorine and color removal Water Cleaning chlorinated pollutants, antibiotics, phenols destruction Water Cleaning chlorinated pollutants, antibiotics, phenols destruction Pesticides Decon major class (thiophosphates) rapidly-completely destroyed Pesticides Decon major class (thiophosphates) rapidly-completely destroyed Chemical Warfare rapid destruction of chemical warfare agents Chemical Warfare rapid destruction of chemical warfare agents Biological Warfare Rapid destruction of anthrax-like spores Biological Warfare Rapid destruction of anthrax-like spores Oxygen Chemistry direct reaction of oxygen with ferric ion Oxygen Chemistry direct reaction of oxygen with ferric ion Peroxidase Mimics first effective peroxide- using enzyme mimics Peroxidase Mimics first effective peroxide- using enzyme mimics High Oxidation state Chemistry synthesis and characterization of rare or unprecedented species High Oxidation state Chemistry synthesis and characterization of rare or unprecedented species Drinking Water Disinfection safer drinking water free of chlorinated disinfection byproducts Drinking Water Disinfection safer drinking water free of chlorinated disinfection byproducts Agricultural animal husbandry, renewable feedstocks Agricultural animal husbandry, renewable feedstocks Others metal refining, carpet recycling, hospital disinfection Others metal refining, carpet recycling, hospital disinfection Laundry dye transfer inhibition, stain removal Laundry dye transfer inhibition, stain removal Mechanism detailed understanding of catalytic mechanism Mechanism detailed understanding of catalytic mechanism Petroleum Refining removal of sulfur contaminants in diesel & gasoline Petroleum Refining removal of sulfur contaminants in diesel & gasoline Pharmaceuticals Decon trace pharmaceuticals removed from water supply Pharmaceuticals Decon trace pharmaceuticals removed from water supply